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EP2632974B1 - Produit stratifié muni d'une couche colorée et procédé de production dudit produit stratifié - Google Patents

Produit stratifié muni d'une couche colorée et procédé de production dudit produit stratifié Download PDF

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Publication number
EP2632974B1
EP2632974B1 EP11773436.8A EP11773436A EP2632974B1 EP 2632974 B1 EP2632974 B1 EP 2632974B1 EP 11773436 A EP11773436 A EP 11773436A EP 2632974 B1 EP2632974 B1 EP 2632974B1
Authority
EP
European Patent Office
Prior art keywords
laminate
layer
polyamide
process according
colour
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP11773436.8A
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German (de)
English (en)
Other versions
EP2632974A1 (fr
Inventor
Markus Parusel
Jonas Scherble
Achim NEUHÄUSER
Ralf Richter
Günther Dickhaut
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Evonik Roehm GmbH
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Filing date
Publication date
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Application filed by Evonik Roehm GmbH filed Critical Evonik Roehm GmbH
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B32B2255/102—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer synthetic resin or rubber layer being a foamed layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2274/00—Thermoplastic elastomer material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4023—Coloured on the layer surface, e.g. ink
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/75—Printability
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/266—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension of base or substrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31562—Next to polyamide [nylon, etc.]

Definitions

  • the present invention relates to a laminate comprising at least one thermoplastic substrate and at least one color layer. Furthermore, the invention describes a method for producing this laminate.
  • Laminates with a color layer are frequently used for the production of decorated plastic components with a special surface quality.
  • the color layer is provided with a reinforcing layer so that a three-layered structure is obtained, wherein the color layer is disposed between the printed substrate and the reinforcing layer.
  • the printed film is crucial for durability.
  • the laminate should have exceptional durability.
  • the laminate should show a chemical resistance that meets very high standards, as these are required for example recently in the field of motor vehicles.
  • the laminate should have a high resistance especially to water-oil or oil-water emulsions such as cosmetics, such as sunscreen.
  • the laminate should be stable to mechanical stress and have a high weathering resistance, a high durability, in particular a high resistance to UV radiation.
  • the laminate should be inexpensive to produce with high and consistent quality. Further, it was an object of the present invention to provide a laminate having a color layer that can be easily formed without significant sacrifice of quality.
  • a printed laminate should be capable of being provided with a reinforcing layer without unacceptably affecting the quality of the colored layer.
  • the present invention accordingly provides a laminate comprising at least one thermoplastic substrate and at least one color layer, which is characterized in that at least one thermoplastic substrate comprises polyamide and has a thickness in the range of 25 microns to 5000 microns, with at least one color layer a polyurethane crosslinking is applied.
  • the laminate of the present invention exhibits an exceptionally good property profile.
  • the laminate has excellent durability.
  • the laminate shows a chemical resistance that meets very high standards, how these are required for example recently in the field of motor vehicles.
  • the laminate has a surprisingly high resistance to water-oil or oil-water emulsions such as cosmetics, for example sunscreen.
  • the laminate is stable to mechanical stress and has a high weathering resistance, a high durability, in particular a high resistance to UV radiation.
  • a laminate according to the invention exhibits a high optical quality, in particular with regard to streaks, stripes, gel bodies and other impurities.
  • a laminate of the present invention can be produced inexpensively with high and consistent quality.
  • a laminate according to the invention with a color layer can be converted easily and without any significant loss of quality.
  • a printed laminate may be provided with a reinforcing layer without unacceptably impairing the quality of the colored layer.
  • the present invention provides a laminate.
  • laminate essentially describes a structure whose thickness is substantially less than its extension in length or width. Accordingly, covered by this term are films and thin moldings.
  • the laminate comprises at least one thermoplastic substrate and at least one color layer.
  • the thermoplastic substrate comprises polyamide.
  • polyamides are thermoplastic polymers whose repeating units are linked via an amide group (-CO-NH-). Surprising advantages are exhibited by polyamides which have been prepared essentially from aromatic, aliphatic or cycloaliphatic dicarboxylic acids and cycloaliphatic diamines. Alternatively, it can also be AB type polyamides, which can be prepared from aminocarboxylic acids. However, preference is given to using polyamides of the AA / BB type from dicarboxylic acids and diamines. In particular, the polyamides may be PA PACM12 or PA MACM12. Furthermore, PA11 or PA12 can be used, reference being made to the usual nomenclature.
  • the polyamides which can be used according to the invention and thus the substrates produced, in particular polyamide molded articles or polyamide films, are preferably prepared by polycondensation essentially from aromatic, cycloaliphatic or aliphatic dicarboxylic acids, preferably from aromatic or aliphatic dicarconic acids and cycloaliphatic diamines.
  • aromatic, cycloaliphatic or aliphatic dicarboxylic acids preferably from aromatic or aliphatic dicarconic acids and cycloaliphatic diamines.
  • up to 40% by weight preferably up to 10% by weight, particularly preferably no further components such as aminoundecanoic acid, monofunctional building blocks or further dicarboxylic acids and / or diamines can be incorporated.
  • it can also be AB type polyamides, which can be prepared from aminocarboxylic acids.
  • polyamides of the AA / BB type can be prepared from dicarboxylic acids and diamines.
  • cycloaliphatic or aliphatic dicarboxylic acids used are cycloaliphatic, partially cyclic aliphatic, linear or branched dicarboxylic acids having 4 to 20, preferably 8 to 16, carbon atoms. Particular preference is given to a dicarboxylic acid having 12 carbon atoms, very particularly preferably to dodecanedioic acid (formula 1):
  • aromatic dicarboxylic acids used are dicarboxylic acids having one or more aromatic rings. Examples are phthalic acid, isophthalic acid or terephthalic acid.
  • the cycloaliphatic diamines are aliphatic diamines having one to three aliphatic rings of 5 to 8, preferably 6 carbons. It is preferably diaminodicyclohexylmethane (formula 2) or 3,3-dimethyl-p-diaminocyclohexylmethane (formula 3):
  • a polyamide which has been prepared essentially from an aliphatic or cycloaliphatic dicarboxylic acid and a cycloaliphatic diamine and has an end group fraction of less than 170 mmol / kg, preferably less than 100 mmol / kg.
  • the carboxyl and / or the amino end group preferably the Aminoend phenomenonanteil less than 100 mmol / kg, more preferably less than 35 mmol / kg.
  • the polyamide which is contained in the substrate is preferably PA PACM12 or PA MACM12.
  • PA PACM12 or PA MACM12 PA PACM12
  • PA MACM12 PA MACM12.
  • TROGAMID® ® particularly in the form of molding compounds from Evonik Degussa GmbH, which is one of these polyamides for example TROGAMID® ® CX7323.
  • polyamides based on aromatic dicarboxylic acids are also preferred embodiments.
  • the substrate may contain other additives, process aids for film production or more Contain plastics. These include stabilizers, plasticizers, fillers such as fibers and dyes.
  • the polyamide content in the substrate is at least 50% by weight, preferably at least 80% by weight and particularly preferably at least 90% by weight, without this being intended to limit it.
  • the substrate with polyamide is, like the laminate, a shaped body whose thickness is substantially less than the extension in length or width, so that the substrate comprising polyamide is generally an extruded semifinished product. Accordingly, the substrate may preferably be in the form of a film, whereby no windability of the substrate is to be implied thereby.
  • the substrate to be provided with a color layer is present in a thickness of 25 to 5000 microns.
  • the thickness is in a range of 50 to 2000 microns, more preferably from 100 to 1000 microns.
  • the coating provided as well as the other side of the substrate may be smooth or have a surface structure, wherein a matte surface of the side to be coated is preferred. For aesthetic reasons, a smooth surface of the uncoated side of the substrate may be preferred.
  • the polyamide-containing shaped bodies or films used as substrates can also be modified during the extrusion process as an alternative to an untreated, transparent and clear film or a corresponding shaped body. Thus, the films or moldings by adding colorants such as pigments and / or dyes be colored.
  • scratch resistance, IR or UV absorption or haptics can be improved or influenced by adding suitable additives.
  • microparticles By adding microparticles, the light scattering can also be changed. Scratch resistance, anti-soiling behavior, antisoiling or altered feel can also be achieved by appropriate coatings.
  • polyamide molded article may also be synonymous with polyamide films.
  • a laminate according to the invention comprises at least one color layer which has a polyurethane crosslinking.
  • the color layer comprises a binder which can be crosslinked via isocyanates.
  • the coating agent used to form the ink layer can be, for example, a printing ink which is rubber-elastic in the dried / cured state and therefore can be deformed during deformation without cracking or deterioration of the optical properties with the film.
  • the binder may therefore preferably contain a cellulose or a cellulose derivative, for example nitrocellulose, a polyurethane, a polyester, a polycarbonate, a polyamide or a poly (meth) acrylate. These polymers can be used singly or as a mixture.
  • the colorant used in the binder may have a weight average molecular weight in the range of 1000 to 50,000 g / mol, more preferably in the range of 2,000 to 20,000 g / mol.
  • the number average of Molecular weight of the binder used is preferably in the range of 1000 to 50,000 g / mol, more preferably in the range of 2,000 to 20,000 g / mol.
  • the number average and weight average molecular weights can be determined by known methods, for example, gel permeation chromatography (GPC), preferably using a PMMA standard.
  • hydroxyl groups which can be crosslinked with isocyanates or isocyanate derivatives to give polyurethanes.
  • binders which before crosslinking have a hydroxyl number in the range from 0.1 to 50 mg KOH / g, more preferably from 0.5 to 30 mg KOH / g.
  • the hydroxyl number can be determined, for example, according to DIN EN ISO 4629.
  • the color layer comprises at least one colorant.
  • a colorant is according to DIN 55943 the collective name for all coloring substances.
  • the colorants include, but are not limited to, soluble dyes and inorganic or organic pigments. These colorants may be used singly or as a mixture of two or more. Thus, in particular mixtures of organic color pigments with soluble organic dyes can be used. Furthermore, it is possible to use mixtures which comprise inorganic and organic color pigments. In addition, mixtures can be used in addition to the inorganic color pigments contain soluble organic dyes. Furthermore, mixtures comprising soluble dyes and inorganic and organic pigments are useful.
  • the colorants set out above are inter alia in Kirk, Othmer Encyclopedia of Chemical Technology, Third Edition, vol. 19, pp. 1 to 78 and in Ullmann's Encyclopedia of Industrial Chemistry 5th edition set out on CD-ROM.
  • colorant depends on the processing of the laminate, whereby a high temperature stability may be required. Accordingly, pigments which are very temperature-stable can preferably be used, so that they do not decompose, sublimate or change the hue due to the temperature which may possibly arise during processing during the injection molding process.
  • the pigments which are preferably contained in the color layer may be any pigments.
  • any pigments for example, but not limited to, titanium dioxide, zinc sulfide, pigment black, azodiaryl yellow, isoindole yellow, diarylid orange, quinacridone magenta, diketopyrrolorot, copper phthalocyanine blue, cullet phthalocyanine green, dioxazine violet, and diketometal oxide may be used.
  • effect pigments such as, but not limited to, metal oxide-coated mica and metallic pigments.
  • the amount of colored pigment is usually 1 to 50% by weight, preferably 3 to 45% by weight, based on the weight of the ink, depending on the kind of the pigment, the desired hiding power and the printing method chosen.
  • White pigment is usually used in an amount of 20 to 50% by weight, preferably 25 to 45% by weight.
  • the colored pigments are often used in an amount of 1 to 20 wt.%, Depending on the type and color shade and the printing method used.
  • Metal oxide-coated mica and metallic pigments are often used in an amount of 1 to 20% by weight, depending on the type and color shade and the printing method used.
  • a primer layer may be provided on the color layer.
  • the adhesion promoter layer is generally matched to the binder used in the color layer and the reinforcing layer to be applied to the adhesion promoter layer.
  • the adhesion promoter layer preferably comprises a cellulose or a cellulose derivative, for example nitrocellulose, a polyurethane, a polyester, a polycarbonate, a polyamide or a poly (meth) acrylate. These polymers can be used singly or as a mixture.
  • a laminate according to the invention may comprise a reinforcing layer wherein the color layer is provided between the thermoplastic substrate and the reinforcing layer.
  • the molding compositions and / or films which can be used for producing the stated reinforcing layer may in particular comprise thermoplastic polymers.
  • the preferred plastics include cellulose or cellulose derivatives, polystyrenes, polystyrene copolymers, such as ABS, polyurethanes, polyesters, polycarbonates, polyamides, polyolefins, in particular polyethylene or polypropylene, polyvinyl chlorides, poly (N-methyl methacrylimides) (PMMI) and / or or polymethylmethacrylate (PMMA). These polymers can be used singly or as a mixture.
  • the reinforcing layer may comprise fillers, in particular fibers.
  • the substrate to be used for producing the present laminate may preferably be obtained by extrusion processes, in particular for the production of semi-finished products, these processes also including film extrusion processes.
  • an extruder with a temperature-controlled nozzle can be used, as this example in FIG. 1 is shown, this extruder comprises a nozzle body (1) with a nozzle lip (2) and a lip gap (3).
  • the nozzle lip (2) is provided with a temperature control (4).
  • the temperature of the die lip (2) between 10 ° C and 100 ° C is preferably higher by 20 ° C to 80 ° C, particularly preferably 30 ° C to 70 ° C, than the temperature of the nozzle body (1).
  • the nozzle body (1) by a maximum of 5 ° C higher, preferably the same temperature as the extruder.
  • the nozzle body (1) generally have a temperature between 250 ° C and 330 ° C.
  • the die lip (2) can simultaneously have a temperature between 290 ° C and 370 ° C.
  • the nozzle lip (2) preferably has an additional temperature control (4).
  • the tempering can be realized for example via inserted heating cartridges or flat radiator. These can u.a. be heated electrically or via a tempered medium such as oil.
  • the temperature can be determined, for example, via thermocouples, resistance thermometers or non-contact temperature measurement methods such as IR thermometers.
  • the indicated temperatures are measured on the inner wall or as close as possible to the inner wall of the extruder cylinder, on the inner wall of the nozzle body or as close as possible to the inner wall of the nozzle body and on the inner wall of the nozzle lip or as close as possible to the inner wall of the nozzle lip.
  • the melt pressure has to be high enough to keep the volatiles still dissolved in the polymer Ingredients, such as water or optionally monomers to keep completely in solution and thus prevent the formation of gas bubbles. This can be ensured, for example, via the geometry of the extrusion die, the content of residual molding material used in the molding composition, the volume flow of melt and the processing temperatures.
  • the extruder used can be any one-, two- or multi-screw extruder suitable for processing polyamides. These extruders can be designed with or without, preferably without, degassing points. The extruders may have several temperature zones or a uniform temperature in the area of the extruder barrel.
  • the polyamide molding composition preferably has a maximum water content of 0.1% by weight, preferably 0.02 Wt.%.
  • the low water content improves the optical quality, in particular with regard to a prevention of blistering and / or turbidity.
  • the molding compound After leaving the extruder, the molding compound is cooled.
  • the cooling process is customarily adapted to the requirements of the laminate.
  • Thin laminates for example films having a thickness of at most 250 ⁇ m, preferably at most 100 ⁇ m, may be produced, inter alia, by the chill-roll process, the melt web being deposited on a cooling roller so that the other side of the film does not have roller contact at that moment. ie there is no counter roll or a Glättspalt.
  • thicker laminates which may have, for example, a thickness of at least 50 .mu.m, preferably at least 100 .mu.m, among other smoothing methods are preferred without this being a restriction.
  • the smoothing process allows a particularly good thickness distribution of the films over extrusion width and particularly good surface qualities, which in turn are dependent on the quality of the roll surface.
  • the plasticized plastic mass emerging from the nozzle is supplied to a calender, the calender comprising a plurality of successively connected rotating rolls about which the plastic mass can be guided, at least two rolls being arranged between these adjacent roll pairs gap is adjustable, by means of which the thickness of the plastic material can be influenced.
  • the setting of the extrusion conditions is selected in the first nip, which adjoins directly to the melt outlet from the nozzle that forms a melt supply / bead, with the finest thickness differences in the Make the film level depending on the location.
  • the number, arrangement and position of the rollers as well as the number of adjacent pairs of rollers over which a shaping gap can be adjusted be designed differently, without this being a restriction.
  • I, F, L and Z arrangements of rolls of the calender are known, wherein in an I-arrangement all rolls are arranged in a line. In the other arrangements, at least one roller is arranged outside a line.
  • a calender with at least three rolls A, C Bundle can be used, wherein the melt can first be applied to a gap 1 between the rolls A and B, so that a melt supply D is formed in the gap 1, as in FIG. 2 exemplified.
  • the roller arrangement of the calender in FIG. 2 corresponds to the I-configuration in a horizontal position.
  • the calender, comprising three rolls A, B and C, a cooling section (E) may be connected downstream, which can withdraw the residual heat from the film.
  • the substrate for example a film may optionally be pretreated.
  • Pretreatments include cleaning with solvents or aqueous cleaners, activation by flame treatment, UV irradiation, corona, plasma or ionized gas treatment such as. As ionized air to reduce dust.
  • the laminate according to the invention comprises a color layer which can be obtained by the application of color.
  • the color comprises at least one curing agent or crosslinking agent which can effect polyurethane crosslinking.
  • the preferred crosslinking agents include in particular polyisocyanates or compounds which release polyisocyanates.
  • Polyisocyanates are compounds having at least 2 isocyanate groups.
  • the polyisocyanates which can be used according to the invention may comprise any desired aromatic, aliphatic and / or cycloaliphatic polyisocyanates.
  • the preferred aromatic polyisocyanates include 1,3- and 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, toluidine diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 4,4'-diphenylmethane diisocyanate, the mixtures of monomeric diphenylmethane diisocyanates (MDI) and oligomeric diphenylmethane diisocyanates (polymer-MDI), xylylene diisocyanate, tetramethylxylylene diisocyanate and triisocyanatotoluene.
  • MDI monomeric diphenylmethane diisocyanates
  • polymer-MDI oligomeric diphenylmethane diisocyanates
  • Preferred aliphatic polyisocyanates have 3 to 16 carbon atoms, preferably 4 to 12 carbon atoms, in the linear or branched alkylene radical and suitable cycloaliphatic or (cyclo) aliphatic diisocyanates advantageously 4 to 18 carbon atoms, preferably 6 to 15 carbon atoms, in the cycloalkylene radical.
  • suitable cycloaliphatic or (cyclo) aliphatic diisocyanates advantageously 4 to 18 carbon atoms, preferably 6 to 15 carbon atoms, in the cycloalkylene radical.
  • (cyclo) aliphatic diisocyanates the skilled worker understands at the same time cyclic and aliphatic bound NCO groups, as z.
  • isophorone diisocyanate is the case.
  • H 12 MDI examples are cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, heptane diisocyanate, octane diisocyanate, nonane diisocyanate, nonane triisocyanate such as 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), decane and triisocyanate, undecanedi and triisocyanate, dodecandi and triisocyanates.
  • TIN 4-isocyanatomethyl-1,8-octane diisocyanate
  • IPDI isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • H 12 MDI diisocyanatodicyclohexylmethane
  • MPDI 2-methylpentane diisocyanate
  • TMDI 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexa-methylene diisocyanate
  • NBDI norbornane diisocyanate
  • Preferred aliphatic, cycloaliphatic and araliphatic, ie aryl-substituted aliphatic diisocyanates are, for example, in Houben-Weyl, Methods of Organic Chemistry, Volume 14/2, pages 61-70 and in the article of W. Siefken, Justus Liebigs Annalen der Chemie 562, pages 75 - 136 described.
  • mixtures of the polyisocyanates can be used.
  • oligoisocyanates or polyisocyanates which are prepared from the abovementioned diisocyanates or polyisocyanates or mixtures thereof by linking by means of urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide, uretonimine , Oxadiazinetrione or iminooxadiazinedione structures.
  • These preferred classes of polyisocyanates can be prepared by dimerization, trimerization, allophanatization, biuretization and / or urethanization of simple diisocyanates.
  • These compounds having more than two isocyanate groups per molecule include, for example, the reaction products of simple diisocyanates, such as. B. IPDI, TMDI, HDI and / or H 12 MDI with polyhydric alcohols (eg., Glycerol, trimethylolpropane, Pentaerythritol) or polyvalent polyamines, or triisocyanurates obtained by trimerization of simple diisocyanates such as IPDI, HDI and H 12 MDI, with HDI-biuret being particularly preferred.
  • simple diisocyanates such as. B. IPDI, TMDI, HDI and / or H 12 MDI
  • polyhydric alcohols eg., Glycerol, trimethylolpropane, Pentaerythritol
  • triisocyanurates obtained by trimerization of simple diisocyanates such as IPDI, HDI and H 12 MDI, with HDI-biuret being particularly preferred.
  • paints which preferably contain from 0.5 to 20% by weight, more preferably from 2 to 10% by weight of crosslinking agent, based on the total weight of the paint.
  • the reaction of the hydroxy groups present in the binder with the organic polyisocyanates may in this case be carried out with 0.5 to 1.1 NCO group per hydroxyl group, depending on the intended use of the reaction products.
  • the reaction is preferably carried out such that the amounts of the organic polyisocyanate, based on the total hydroxy content of the components present in the reaction mixture per hydroxyl group, are present in an amount of from 0.7 to 1.0 isocyanate groups.
  • the paint may contain other common solvents, additives and / or processing aids, these components being custom tuned to the printing technology and application requirements.
  • Particularly suitable printing inks are available, for example, from Pröll KG, Weissenburg in Bavaria, DE, under the name NoriAmid®.
  • the color set out above can be applied to the substrate by known methods, preferably printing methods.
  • Suitable printing methods for applying printing ink layers are known, in principle all printing methods such as high-pressure, intaglio, flexographic printing, offset printing, screen printing, pad printing, digital printing, in particular inkjet printing and laser printing are suitable. Gravure printing, flexographic printing and screen printing are preferred, screen printing being particularly preferred. With regard to screen printing, flatbed screen printing is preferred. These printing methods are used inter alia Kipphan, Handbook of Print Media, Springer-Verlag, Berlin, 2000, ISBN-10 3540669418 These methods are incorporated in this application for purposes of disclosure.
  • the coating is cured by conventional methods and dried using solvents.
  • the curing or drying time may vary depending on the type and amount of the solvent and the degree of crosslinking.
  • the curing or drying time is so chosen that the color layer retains a sufficient elasticity for a possible forming process, but is so strongly crosslinked that the color layer has sufficient for a possible transformation and further action strength.
  • a drying or curing time of at least 5 minutes, more preferably at least 10 minutes and most preferably at least 20 minutes at temperatures of about 50 ° C or, depending on the dryer, 90 ° C often leads to a sufficiently high stability of the ink layer. For these reasons, the drying time should not take too long, otherwise a brittleness of the ink layer may occur, which complicates a transformation.
  • the curing depends on the temperature. At 50 ° C, therefore, surprising advantages can be obtained if the drying time is at most 20 hours, preferably at most 10 hours. A higher temperature can accelerate the drying process, so that at 90 ° C, the drying time is preferably at most 5 hours, preferably at most 4 hours.
  • the primer layer may be dried together with the ink, whereby curing of the ink may occur during drying of the primer layer.
  • the adhesion promoter layer can be applied to the substrate by the same methods as the color layer, wherein the color layer and the adhesion promoter layer are particularly preferably printed by screen printing, in particular flatbed screen printing.
  • Printed laminates produced according to the invention preferably polyamide films, particularly preferably flexible polyamide films, can be u. a. for lamination to molding compounds, wood, glass or metals, preferably molding compounds are used.
  • the lamination can be done for example by gluing on a surface of the laminate, wherein the lamination can be done on the printed or unprinted side.
  • the hot lamination of the film on another film or on a plate is possible.
  • the films of the invention can also be laminated with one or more carrier films.
  • the substrate provided with a cross-linked ink layer can be reformed by known methods, the nature of the transformation process and the process parameters depending on the application and the properties of the laminate.
  • the laminate according to the invention can be brought into a mold by deep-drawing, thermoforming or high-pressure deformation.
  • the polyamide film can be back-injected with one or more polymeric materials, such as a molding compound. This can be done in particular after a forming. Alternatively, of course, moldings obtainable from the molding compound and the laminate, which may optionally be formed, can be bonded together.
  • the optionally formed laminate can be back-injected by conventional injection molding.
  • Common injection molding materials which can be used to back coat the laminate comprising a crosslinked dye layer are, but are not limited to, polyamides, polyesters, polycarbonates, polystyrenes, polystyrene copolymers such as ABS, poly ( N-methylmethacrylimides) (PMMI) and / or polymethyl methacrylates (PMMA).
  • Preferred material for injection molding are polyamides or polymethyl methacrylates.
  • the laminates may be subjected to one or more of the following processing steps:
  • processing of the film is not limited to the mentioned methods.
  • the processing methods may be used in a different order than that mentioned. Likewise, processing steps can also be repeated one or more times.
  • the water content was determined according to Karl Fischer.
  • the end group determinations are carried out by means of titration.
  • the production of the polyamide film was carried out by methods known per se, such as, for example, extrusion through a slot die, as in flat film extrusion, blown film extrusion, or by solution casting.
  • the plastic molding can also be made as a multilayer by adhesion extrusion coating or lamination in subsequent process steps.
  • the examples were prepared on a commercially available flat film system from Collin. This was the polyamide is preferably introduced in granular form into a funnel, from which it is conveyed into the extruder.
  • the extruder consisted of a usually metallic cylinder heated from the outside and an extruder screw which rotated in the extruder on its own axis and thus conveyed the polymer from the draw-in area behind the hopper opening through the extruder.
  • twin or multi-screw extruders may also be used.
  • the polymer Due to the heating from the outside and the shearing of the polymer in the extruder, the polymer melted and got behind the tip of the extruder screw in the extrusion die in the form of the film die (or in general: wide-slot tool).
  • the polyamide melt was converted into a flat shape and exited through the nozzle gap surface of the film die.
  • the film die can also be fed with melt from several extruders, thereby producing multilayer films. Subsequently, the plastic sheet was cooled on at least one roller and subsequently wound up.
  • the closed-cylinder extruder used for the experiments two extruder zones temperature-controlled and no vent, had a screw diameter of 35 mm with an L / D ratio (screw length / screw diameter) of 25.
  • L / D ratio screw length / screw diameter
  • the films were produced in the test setup in a single layer in the so-called chill-roll process and have a thickness of 50 microns. Subsequently, the films were visually evaluated for their quality. For this purpose, the films were optically compared and evaluated in terms of optical quality compared to a reference pattern in marketable quality. Under optical quality here u.a. the sizes strip, surface quality, Gel Sciencesanress, number of impurities and number of particles of degraded material to understand. All the samples considered to be marketable received the rating (+). The samples, which were barely marketable, received the rating (o) and the samples that were clearly or very clearly non-marketable received the ratings (-) and (-), respectively.
  • polyamide PA1 it was Polyamide PA PACM 12 from Evonik Degussa GmbH, for example, based on the composition of the TROGAMID® ® CX7323.
  • Polyamide PA2 is a medium viscosity PA PACM 12. example Material film quality Water content according to KF Aminoendgr. mmol / kg Carboxylendgr.
  • the prepared film was printed with commercially available printing inks from Pröll KG, which enable isocyanate crosslinking, using a screen printing process (NoriAmid®).
  • the inks were mixed with an isocyanate hardener (Hardener 8125, available from Pröll KG) and treated with a thinner (SMK 090, available from Pröll KG) to adjust the viscosity to the viscosity requirements.
  • a primer layer (NoriAmid® APM, available from Pröll KG) was applied.
  • the printing was done without preheating with a 100-40y fabric.
  • the foil inserts are back-injected with TROGAMID® CX 7323 and oriented with Makrolon® 2205.
  • a laminate having an excellent property profile was obtained, which satisfies both high aesthetic requirements and exhibits excellent resistance to chemical and mechanical stresses.

Landscapes

  • Laminated Bodies (AREA)

Claims (14)

  1. Stratifié, comprenant au moins un substrat thermoplastique et au moins une couche colorée, caractérisé en ce qu'au moins un substrat thermoplastique comprend du polyamide et présente une épaisseur dans la plage de 25 µm à 5000 µm, sur lequel est appliquée au moins une couche colorée présentant une réticulation de type polyuréthane.
  2. Stratifié selon la revendication 1, caractérisé en ce que le stratifié présente une couche de promoteur d'adhérence qui est appliquée sur la couche colorée.
  3. Stratifié selon la revendication 1 ou 2, caractérisé en ce que le stratifié présente une couche de renforcement, la couche colorée étant prévue entre le substrat thermoplastique et la couche de renforcement.
  4. Procédé pour la préparation d'un stratifié selon au moins l'une quelconque des revendications 1 à 3, caractérisé en ce qu'un substrat thermoplastique plan, comprenant un polyamide présentant une épaisseur dans la plage de 25 µm à 5000 µm est pourvu d'une couche colorée, le liant présent dans la couleur étant réticulé par des polyisocyanates.
  5. Procédé selon la revendication 4, caractérisé en ce que le liant présente une moyenne pondérale du poids moléculaire dans la plage de 1000 g/mole à 50 000 g/mole.
  6. Procédé selon la revendication 4 ou 5, caractérisé en ce que le liant présente un indice d'hydroxyle de 0,1 à 50 mg de KOH/g.
  7. Procédé selon au moins l'une quelconque des revendications 4 à 6, caractérisé en ce que le liant comprend de la cellulose ou un dérivé de cellulose, un polyuréthane, un polyester, un polycarbonate, un polyamide ou un poly(méth)acrylate.
  8. Procédé selon au moins l'une quelconque des revendications 4 à 7, caractérisé en ce qu'on utilise un polyisocyanate aliphatique pour la réticulation.
  9. Procédé selon au moins l'une quelconque des revendications 4 à 8, caractérisé en ce que la couleur est imprimée au moyen d'un procédé de sérigraphie sur la feuille de polyamide.
  10. Procédé selon au moins l'une quelconque des revendications 4 à 9, caractérisé en ce qu'une couche de promoteur d'adhérence est appliquée sur la couche colorée obtenue par l'impression par la couleur.
  11. Procédé selon la revendication 10, caractérisé en ce que le promoteur d'adhérence comprend de la cellulose ou un dérivé de cellulose, un polyuréthane, un polyester, un polycarbonate, un polyamide ou un poly(méth)acrylate.
  12. Procédé selon la revendication 10 ou 11, caractérisé en ce que le promoteur d'adhérence est imprimé au moyen d'un procédé de sérigraphie sur la couche colorée.
  13. Procédé selon au moins l'une quelconque des revendications 4 à 12, caractérisé en ce que la feuille de polyamide imprimée est transformée.
  14. Procédé selon au moins l'une quelconque des revendications 4 à 13, caractérisé en ce que la feuille de polyamide imprimée est pourvue d'une couche de renforcement.
EP11773436.8A 2010-10-25 2011-10-11 Produit stratifié muni d'une couche colorée et procédé de production dudit produit stratifié Revoked EP2632974B1 (fr)

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PCT/EP2011/067668 WO2012055697A1 (fr) 2010-10-25 2011-10-11 Produit stratifié muni d'une couche colorée et procédé de production dudit produit stratifié

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EP (1) EP2632974B1 (fr)
JP (1) JP2013543800A (fr)
KR (1) KR20130100895A (fr)
CN (1) CN102782025A (fr)
BR (1) BR112013009992A2 (fr)
CA (1) CA2815709A1 (fr)
IL (1) IL221052A0 (fr)
SG (1) SG189005A1 (fr)
TW (1) TW201231280A (fr)
WO (1) WO2012055697A1 (fr)
ZA (1) ZA201205961B (fr)

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FR3005660B1 (fr) * 2013-05-17 2015-04-24 Arkema France Procede de reticulation en surface de particules de polymere
EP3824913A1 (fr) 2019-11-19 2021-05-26 Evonik Operations GmbH Matière de moulage paek remplie de verre

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WO2004085558A1 (fr) 2003-03-21 2004-10-07 E. I. Du Pont De Nemours And Company Compositions de revetement a base de diol d'ether de polytrimethylene

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WO2012055697A1 (fr) 2012-05-03
SG189005A1 (en) 2013-05-31
CN102782025A (zh) 2012-11-14
TW201231280A (en) 2012-08-01
JP2013543800A (ja) 2013-12-09
BR112013009992A2 (pt) 2019-09-24
ZA201205961B (en) 2013-09-25
EP2632974A1 (fr) 2013-09-04
KR20130100895A (ko) 2013-09-12
IL221052A0 (en) 2012-09-24
US20130216827A1 (en) 2013-08-22
CA2815709A1 (fr) 2012-05-03

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